CN119278237A

CN119278237A - Anti-drip polycarbonate composition

Info

Publication number: CN119278237A
Application number: CN202380042811.5A
Authority: CN
Inventors: 彼得·亨德里克斯·特奥多鲁斯·福伦贝格; 汤姆·L·埃文斯
Original assignee: SABIC Global Technologies BV
Current assignee: SABIC Global Technologies BV
Priority date: 2022-05-25
Filing date: 2023-05-25
Publication date: 2025-01-07
Also published as: EP4532605A1; WO2023228123A1

Abstract

The polycarbonate composition comprises a linear homopolycarbonate and optionally a styrene-containing copolymer, a poly (carbonate-siloxane) comprising about 10wt% to less than about 30wt% siloxane, present in an amount effective to provide about 1 to about 6wt% siloxane based on the total weight of the composition, an ultra-high molecular weight polydimethylsiloxane, present in an amount effective to provide greater than about 0.3 to less than about 0.9wt% siloxane based on the total weight of the composition, a flame retardant, and optionally an additive composition. A molded sample of the polycarbonate composition has a UL94 fire test rating or V-0 at a thickness of 1.5mm, exhibits anti-drip properties, and can be substantially halogen free, i.e., the polycarbonate composition comprises less than about 900 parts per million (ppm) of each of chlorine, bromine, and optionally fluorine, and further comprises less than about 1500ppm total chlorine, bromine, and fluorine content.

Description

Anti-drip polycarbonate compositions

Technical Field

The present disclosure relates to polycarbonate compositions, and more particularly, to anti-drip polycarbonate compositions, methods of manufacture, and uses thereof.

Background

Polycarbonates are useful in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic appliances. Because of their wide range of applications, it is desirable to provide polycarbonates that are flame retardant when molded into articles.

Accordingly, there remains a need in the art for polycarbonate compositions that are flame retardants. It would be a further advantage if the composition was substantially halogen-free.

Disclosure of Invention

The above and other deficiencies in the art are met by a polycarbonate composition comprising a linear homopolycarbonate and optionally a copolymer comprising styrene, a poly (carbonate-siloxane) comprising from about 10wt% to less than about 30wt% of a siloxane, present in an amount effective to provide a siloxane content of from about 1wt% to about 6wt% based on the total weight of the polycarbonate composition, an ultra-high molecular weight polydimethylsiloxane, present in an amount effective to provide a siloxane content of from greater than about 0.3wt% to less than about 0.9wt% based on the total weight of the composition, wherein the weight average molecular weight of the polydimethylsiloxane is at least 100,000 grams/mole as determined by gel permeation chromatography according to polystyrene standards, a flame retardant, and optionally an additive composition, wherein the linear homopolycarbonate, the optional styrene-containing copolymer, the poly (carbonate-siloxane), the ultra-high molecular weight polydimethylsiloxane, the flame retardant, and the optional additive composition add up to 100wt%.

In another aspect, a method of manufacture includes combining the above components to form a polycarbonate composition.

In yet another aspect, an article comprises the polycarbonate composition described above.

In yet another aspect, a method of making an article comprises molding, extruding, or shaping the polycarbonate composition described above into an article.

The above described and other features are exemplified by the following detailed description, examples and claims.

Detailed Description

Due to miniaturization and market trends of electronic components, there is a need for flame retardant articles that are substantially halogen free. As used herein, the phrase "substantially halogen-free" is defined by IEC 61249-2-21 or UL 746H. According to the International electrotechnical Commission, halogen limitation use (IEC 61249-2-21), the composition should contain less than 900ppm (ppm) of each of chlorine and bromine, and also contain less than 1500ppm total bromine, chlorine and fluorine content. According to UL 746H, the composition should contain less than 900ppm of each of chlorine, bromine and fluorine and less than 1500ppm of total chlorine, bromine and fluorine content. Bromine, chlorine and fluorine content (in ppm) can be calculated from the composition or measured by elemental analysis techniques. Conventional flame retardants may or may not include halogen, but commonly employed anti-drip agents include PTFE-encapsulated styrene-acrylonitrile copolymers (e.g., TSAN) and thus include fluorine. Flame retardants that are not brominated, chlorinated, or fluorinated have been used in conventional polycarbonate compositions, but typically are present in combination with flame retardants such that the halogen content of the composition exceeds the 1500ppm total halogen limit according to IEC 61249-2-21 and UL 746H. Similarly, when non-brominated or chlorinated but fluorinated flame retardants are used in combination with fluorinated anti-drip agents, the halogen content of the composition exceeds the 1500ppm total halogen limit due to the presence of fluorine according to IEC 61249-2-21 or UL 746H. It would therefore be particularly advantageous if the anti-drip agent was non-fluorinated such that the anti-drip agent would not contribute a halogen content to the total halogen content of the composition. When a non-fluorinated anti-drip agent is used, a variety of flame retardants, including or excluding halogens, may be used in combination with the non-fluorinated anti-drip agent such that the composition may be considered "substantially halogen free" according to IEC 61249-2-21 or UL 746H.

The inventors have found that polycarbonate compositions comprising a linear homopolycarbonate and optionally a copolymer comprising styrene, a flame retardant, a poly (carbonate-siloxane) and an ultra high molecular weight polydimethylsiloxane can provide anti-drip properties without compromising flame retardancy, e.g., UL-94 burn test rating. Advantageously, at a thickness of 1.5mm or 2.9mm, the polycarbonate composition may have a UL-94 burn test rating of V-0, no dripping, and is considered "substantially halogen-free" according to IEC 61249-2-21 or UL 746H. A further advantage is that V-0 burn test rating and anti-drip performance are not achieved at the expense of the aesthetic quality of molded samples of polycarbonate compositions. In practice, the polycarbonate composition may contain a colorant to provide a colored article, such as, for example, a white or black article.

As used herein, "polycarbonate" refers to a polymer having repeating structural carbonate units of formula (1):

Wherein at least 60% of the total number of R ¹ groups comprise aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic. In one aspect, each R ¹ is a C _6-30 aromatic group, i.e., comprising at least one aromatic moiety. R ¹ may be derived from the formula HO-R ¹ -OH, in particular an aromatic dihydroxy compound of formula (2):

HO-A¹-Y¹-A²-OH(2)

Wherein a ¹ and a ² are each a monocyclic divalent aromatic group and Y ¹ is a single bond or a bridging group having one or more atoms that separate a ¹ from a ². In one aspect, one atom separates a ¹ from a ². Preferably, each R ¹ may be derived from a bisphenol of formula (3):

Wherein R ^a and R ^b are each independently halogen, C _1-12 alkoxy, or C _1-12 alkyl, and p and q are each independently integers from 0 to 4. it will be appreciated that when p or q is less than 4, the valence of each carbon of the ring is filled with hydrogen. Also in formula (3), X ^a is a bridging group linking the two hydroxy-substituted aromatic groups, wherein the bridging group and the hydroxy substituent of each C ₆ arylene group are disposed ortho, meta, or para (preferably para) to each other on the C ₆ arylene group. In one aspect, bridging group X ^a is a single bond, -O-, -S (O) ₂ -, -C (O) -, or C _1-60 organic group. The organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon, or phosphorus. The C _1-60 organic groups may be arranged such that the C ₆ arylene groups attached thereto are each attached to a common alkylidene carbon or to different carbons of the C _1-60 organic bridging group. In one aspect, p and q are each 1, and R ^a and R ^b are each a C _1-3 alkyl group, preferably methyl, disposed meta to the hydroxy group on each arylene group.

In one aspect, X ^a is C _3-18 cycloalkylidene, a C _1-25 alkylidene of the formula-C (R ^c)(R^d) -wherein R ^c and R ^d are each independently hydrogen, C _1-12 alkyl, C _1-12 cycloalkyl, C _7-12 aralkyl, C _1-12 heteroalkyl, or cyclic C _7-12 heteroaralkyl, or a group of the formula-C (=r ^e) -wherein R ^e is a divalent C _1-12 hydrocarbon group. These types of groups include methylene, cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, as well as 2- [2.2.1] -bicycloheptylidene, cyclohexylidene, 3-dimethyl-5-methylcyclohexylidene, cyclopentylidene, cyclododecylidene, and adamantylidene.

In another aspect, X ^a is C _1-18 alkylene, C _3-18 cycloalkylene, fused C _6-18 cycloalkylene, or a group of formula-J ¹-G-J² ", wherein J ¹ and J ² are the same or different C _1-6 alkylene groups, and G is C _3-12 cycloalkylidene or C _6-16 arylene.

For example, X ^a can be a substituted C _3-18 cycloalkylidene group of formula (4):

Wherein R ^r、R^p、R^q, and R ^t are each independently hydrogen, halogen, oxygen, or C _1-12 hydrocarbyl, Q is a direct bond, carbon, or divalent oxygen, sulfur, or-N (Z) -, where Z is hydrogen, halogen, hydroxy, C _1-12 alkyl, C _1-12 alkoxy, C _6-12 aryl, or C _1-12 acyl, R is 0 to 2, t is 1 or 2, q is 0 or 1, and k is 0 to 3, provided that R ^r、R^p、R^q, and at least two of R ^t taken together are a fused alicyclic, aromatic, or heteroaromatic ring. It will be appreciated that when the fused ring is aromatic, the ring shown in formula (4) will have an unsaturated carbon-carbon bond wherein the ring is fused. When k is 1 and q is 0, the ring shown in formula (4) contains 4 carbon atoms, when k is 2, the ring shown in formula (4) contains 5 carbon atoms, and when k is 3, the ring contains 6 carbon atoms. In one aspect, two adjacent groups (e.g., R ^q and R ^t together) form an aromatic group, and in another aspect, R ^q and R ^t together form one aromatic group and R ^r and R ^p together form a second aromatic group. When R ^q and R ^t together form an aromatic group, R ^p may be a double bond oxygen atom, i.e. a ketone, or Q may be-N (Z) -, where Z is phenyl.

Bisphenols, wherein X ^a is a cycloalkylidene group of formula (4), may be used to prepare polycarbonates comprising benzopyrrolidone carbonate units of formula (1 a):

Wherein R ^a、R^b, p and q are as in formula (3), R ³ are each independently C _1-6 alkyl, j is 0 to 4, and R ₄ is hydrogen, C _1-6 alkyl, or substituted or unsubstituted phenyl, e.g., phenyl substituted with up to 5C _1-6 alkyl groups. For example, the benzopyrrolidone carbonate unit has formula (1 b):

Wherein R ⁵ is hydrogen, phenyl optionally substituted with up to five C _1-6 alkyl groups or C _1-4 alkyl groups. In one aspect of formula (1 b), R ⁵ is hydrogen, methyl, or phenyl, preferably phenyl. Carbonate unit (1 b), wherein R ⁵ is phenyl can be derived from 2-phenyl-3, 3' -bis (4-hydroxyphenyl) phthalimidine (also known as 3, 3-bis (4-hydroxyphenyl) -2-phenylisoindolin-1-one, or N-phenylphenol phthalide bisphenol).

Other bisphenol carbonate repeat units of this type are isatin carbonate units of the formulae (1 c) and (1 d):

Wherein R ^a and R ^b are each independently halogen, C _1-12 alkoxy, or C _1-12 alkyl, p and q are each independently 0 to 4, and R ⁱ is C _1-12 alkyl, phenyl optionally substituted with 1 to 5C _1-10 alkyl, or benzyl optionally substituted with 1 to 5C _1-10 alkyl. In one aspect, R ^a and R ^b are each methyl, p and q are each independently 0 or 1, and R ⁱ is C _1-4 alkyl or phenyl.

Other embodiments of bisphenol carbonate units derived from bisphenol (3) wherein X ^a is substituted or unsubstituted C _3-18 cycloalkylidene, including cyclohexylidene-bridged bisphenols of formula (1 e):

Wherein R ^a and R ^b are each independently C _1-12 alkyl, R ^g is C _1-12 alkyl, p and q are each independently 0 to 4, and t is 0 to 10. In a particular aspect, at least one of each of R ^a and R ^b is arranged meta to the cyclohexylidene bridging group. In one aspect, R ^a and R ^b are each independently C _1-4 alkyl, R ^g is C _1-4 alkyl, p and q are each 0 or 1, and t is 0 to 5. In another particular aspect, R ^a、R^b and R ^g are each methyl, p and q are each 0 or 1, and t is 0 or 3, preferably 0. In yet another aspect, p and q are each 0, each R ^g is methyl, and t is 3, such that X ^a is 3, 3-dimethyl-5-methylcyclohexylidene.

Examples of other bisphenol carbonate units derived from bisphenol (3) wherein X ^a is a substituted or unsubstituted C _3-18 cycloalkylidene group comprising adamantyl units of formula (1 f) and fluorenyl units of formula (1 g)

Wherein R ^a and R ^b are each independently C _1-12 alkyl and p and q are each independently 1 to 4. In a particular aspect, at least one of each R ^a and R ^b is disposed meta to the cycloalkylidene bridging group. In one aspect, R ^a and R ^b are each independently C _1-3 alkyl and p and q are each 0 or 1, preferably R ^a、R^b is each methyl and p and q are each 0 or 1, and when p and q are 1, the methyl group is disposed meta to the cycloalkylidene bridging group. The carbonates comprising units (1 a) to (1 g) can be used for the production of polycarbonates having a high glass transition temperature (Tg) and a high heat distortion temperature.

Other useful dihydroxy compounds of the formula HO-R ¹ -OH include aromatic dihydroxy compounds of the formula (6):

Wherein each R ^h is independently a halogen atom, a C _1-10 hydrocarbyl group such as C _1-10 alkyl, halogen substituted C _1-10 alkyl, C _6-10 aryl, or halogen substituted C _6-10 aryl, and n is 0 to 4. The halogen is typically bromine.

Some illustrative examples of specific dihydroxy compounds include 4,4' -dihydroxybiphenyl, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1, 2-bis (4-hydroxyphenyl) ethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 2-bis (4-hydroxy-3-bromophenyl) propane, 1-bis (hydroxyphenyl) cyclopentane, 1, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) isobutylene, 1-bis (4-hydroxyphenyl) cyclododecane, trans-2, 3-bis (4-hydroxyphenyl) -2-butene, 2-bis (4-hydroxyphenyl) adamantane, alpha, alpha' -bis (4-hydroxyphenyl) toluene, bis (4-hydroxyphenyl) acetonitrile, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3-ethyl-4-hydroxyphenyl) propane, 2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2, 2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2-bis (3-allyl-4-hydroxyphenyl) propane, 2-bis (3-methoxy-4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) hexafluoropropane, 1, 1-dichloro-2, 2-bis (4-hydroxyphenyl) ethylene, 1-dibromo-2, 2-bis (4-hydroxyphenyl) ethylene, 1-dichloro-2, 2-bis (5-phenoxy-4-hydroxyphenyl) ethylene, 4,4' -dihydroxybenzophenone, 3-bis (4-hydroxyphenyl) -2-butanone, 1, 6-bis (4-hydroxyphenyl) -1, 6-hexanedione, ethylene glycol bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, 9, 9-bis (4-hydroxyphenyl) fluoro, 2, 7-dihydroxypyrene, 6' -dihydroxy-3, 3' -tetramethylspiro (bis) indane ("spirobiindane bisphenol"), 3-bis (4-hydroxyphenyl) phthalimide, 2, 6-dihydroxydibenzo-p-dioxin, 2, 6-dihydroxythianthrene, 2, 7-dihydroxyphenothiazine, 2, 7-dihydroxy-9, 10-dimethylphenoxazine, 3, 6-dihydroxydibenzofuran, 3, 6-dihydroxydibenzothiophene, and 2, 7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-tert-butylresorcinol, 5-phenylresorcinol, 5-cumylresorcinol, 2,4,5, 6-tetrafluororesorcinol, 2,4,5, 6-tetrabromoresorcinol, and the like, catechols, hydroquinones, substituted hydroquinones such as 2-methylhydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5, 6-tetramethyl hydroquinone, 2,3,5, 6-tetra-t-butyl hydroquinone, 2,3,5, 6-tetrafluoro hydroquinone, 2,3,5, 6-tetrabromo hydroquinone, and the like, or combinations thereof.

Specific examples of bisphenol compounds of formula (3) include 1, 1-bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) propane (hereinafter "bisphenol A" or "BPA"), 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, 1-bis (4-hydroxyphenyl) propane 1, 1-bis (4-hydroxyphenyl) n-butane, 2-bis (4-hydroxy-2-methylphenyl) propane, 1-bis (4-hydroxy-tert-butylphenyl) propane, 3-bis (4-hydroxyphenyl) phthalimidine, 2-phenyl-3, 3-bis (4-hydroxyphenyl) phthalimidine (PPPBP), and 1, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane (DMBPC). Combinations may also be used. In a particular aspect, the polycarbonate is a linear homopolymer derived from bisphenol A, in which each of A ¹ and A ² is p-phenylene and Y ¹ is isopropylidene in formula (3).

The polycarbonate composition may comprise bisphenol a polycarbonate homopolymer, also referred to as bisphenol a homopolycarbonate. Bisphenol A polycarbonate homopolymer has repeating structural carbonate units of formula (1).

Polycarbonates may be prepared by known methods such as interfacial polymerization and melt polymerization, which are known and described, for example, in WO 2013/175448 A1 and WO 2014/072923 A1. End-capping agents (also referred to as chain terminators or chain terminators) may be included during polymerization to provide end groups, for example monocyclic phenols such as phenol, p-cyanophenol and C _1-22 alkyl-substituted phenols such as p-cumylphenol, resorcinol monobenzoate, and p-butylphenol and t-butylphenol, monoethers of dihydric phenols such as p-methoxyphenol, monoesters of dihydric phenols such as resorcinol monobenzoate, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryloyl chloride, and monochloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumylphenyl chloroformate and toluene chloroformate. Combinations of different end groups may be used. Branched polycarbonate blocks may be prepared by adding branching agents during the polymerization process, such as trimellitic acid, trimellitic anhydride, trimellitic chloride, tris-p-hydroxyphenylethane, isatin-bisphenol, triphenoltc (1, 3, 5-tris ((p-hydroxyphenyl) isopropyl) benzene), triphenolpa (4 (4 (1, 1-bis (p-hydroxyphenyl) -ethyl) α, α -dimethylbenzyl) phenol), 4-chloroformylphthalic anhydride, trimesic acid and benzophenone tetracarboxylic acid. The branching agent may be added at a level of 0.05 to 4.0wt% (wt%), for example, 0.05 to 2.0 wt%. Combinations comprising linear polycarbonates and branched polycarbonates may be used.

The polycarbonates may have an intrinsic viscosity of 0.3 to 1.5 deciliters per gram (dl/gm), preferably 0.45 to 1.0dl/gm, measured in chloroform at 25 ℃. The polycarbonates may have a weight average molecular weight (Mw) of 10,000 to 200,000 g/mol, preferably 20,000 to 100,000g/mol, measured by Gel Permeation Chromatography (GPC) using crosslinked styrene-divinylbenzene columns, based on polystyrene standards and calculated to the polycarbonate. GPC samples were prepared at a concentration of 1mg/ml, and eluted at a flow rate of 1.5 ml/min. The linear homopolycarbonate may comprise bisphenol a polycarbonate homopolymer. The linear bisphenol a polycarbonate homopolymer may have a weight average molecular weight of 15,000 to 25,000g/mol, preferably 17,000 to 25,000g/mol, as determined by GPC according to polystyrene standards and calculated for the polycarbonate. The linear bisphenol A polycarbonate homopolymer may have a weight average molecular weight of 26,000 to 40,000g/mol, preferably 27,000 to 35,000g/mol, as determined by GPC according to polystyrene standards and calculated for the polycarbonate.

In one aspect, more than one linear homopolycarbonate may be present. For example, the linear homopolycarbonate may include bisphenol A homopolycarbonate having a weight average molecular weight of 15,000 to 25,000g/mol or 17,000 to 23,000g/mol or 18,000 to 22,000g/mol, and bisphenol A homopolycarbonate having a weight average molecular weight of 26,000 to 40,000g/mol or 26,000 to 35,000g/mol, each measured by GPC according to polystyrene standards and calculated for the polycarbonate. The weight ratio of linear homopolycarbonates to each other is from 10:1 to 1:10, preferably from 5:1 to 1:5, more preferably from 3:1 to 1:3, or from 2:1 to 1:2.

In addition to the linear homopolycarbonate, the polycarbonate composition may include a styrene-containing copolymer in combination with the linear homopolycarbonate. The styrene-containing copolymer comprises an elastomeric phase comprising (i) butadiene and having a Tg of less than about 10 ℃, and (ii) a rigid polymer phase having a Tg of greater than about 15 ℃ and comprising a copolymer of a monovinylaromatic monomer comprising styrene and an unsaturated nitrile such as acrylonitrile. The styrene-containing copolymer may include a monovinylaromatic monomer other than styrene. Such styrene-containing copolymers may be prepared by first providing an elastomeric polymer and then polymerizing the constituent monomers of the rigid phase in the presence of the elastomer to obtain a graft copolymer. The grafts may be attached to the elastomeric core as graft branches or as shells. The shell may simply physically encapsulate the core, or the shell may be partially or substantially completely grafted to the core.

Polybutadiene homopolymers may be used as the elastomeric phase. Alternatively, the elastomeric phase of the styrene-containing copolymer comprises butadiene copolymerized with up to about 25wt% of another conjugated diene monomer of formula (8):

Wherein each X ^b is independently C ₁-C₅ alkyl. Examples of conjugated diene monomers that may be used are isoprene, 1, 3-heptadiene, methyl-1, 3-pentadiene, 2, 3-dimethyl-1, 3-butadiene, 2-ethyl-1, 3-pentadiene, 1, 3-and 2, 4-hexadienes and the like, as well as mixtures comprising at least one of the foregoing conjugated diene monomers. A specific conjugated diene is isoprene.

The elastomeric butadiene phase may additionally be copolymerized with up to 25wt%, preferably up to about 15wt%, of another comonomer, for example a monovinylaromatic monomer containing condensed aromatic ring structures, such as vinylnaphthalene, vinylanthracene, etc., or a monomer of formula (9):

Wherein each X ^c is independently hydrogen, C ₁-C₁₂ alkyl, C ₃-C₁₂ cycloalkyl, C ₆-C₁₂ aryl, C ₇-C₁₂ aralkyl, C ₇-C₁₂ alkaryl, C ₁-C₁₂ alkoxy, C ₃-C₁₂ cycloalkoxy, C ₆-C₁₂ aryloxy, chloro, bromo, or hydroxy, and R is hydrogen, C ₁-C₅ alkyl, bromo, or chloro. Examples of suitable monovinyl aromatic monomers copolymerizable with butadiene include styrene, 3-methylstyrene, 3, 5-diethylstyrene, 4-n-propylstyrene, alpha-methylstyrene, alpha-methyl vinyltoluene, alpha-chlorostyrene, alpha-bromostyrene, dichlorostyrene, dibromostyrene, tetrachlorostyrene, and the like, as well as combinations comprising at least one of the foregoing monovinyl aromatic monomers. In one aspect, butadiene is copolymerized with up to about 12wt%, preferably from about 1wt% to about 10wt%, of styrene and/or alpha-methylstyrene.

Other monomers which can be copolymerized with butadiene are monovinyl monomers such as itaconic acid, acrylamide, N-substituted acrylamides or methacrylamides, maleic anhydride, maleimides, N-alkyl-, aryl-, or haloaryl-substituted maleimides, glycidyl (meth) acrylates, and monomers of the formula (10):

wherein R is hydrogen, C ₁-C₅ alkyl, bromo or chloro, and X ^c is cyano, C ₁-C₁₂ alkoxycarbonyl, C ₁-C₁₂ aryloxycarbonyl, hydroxycarbonyl, or the like. Examples of monomers of formula (10) include acrylonitrile, ethacrylonitrile, methacrylonitrile, α -chloroacrylonitrile, β -chloroacrylonitrile, α -bromoacrylonitrile, acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like, as well as combinations comprising at least one of the foregoing monomers. Monomers such as n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate are generally used as monomers copolymerizable with butadiene.

The particle size of the butadiene phase is not limited and may be, for example, from about 0.01 to about 20 microns, preferably from about 0.5 to about 10 microns, more preferably from about 0.6 to about 1.5 microns, may be used for the bulk polymerized rubber matrix. Particle size may be measured by light transmission or capillary hydrodynamic Chromatography (CHDF). The butadiene phase may provide from about 5wt% to about 95wt% of the total weight of the styrene-containing copolymer, more preferably from about 20wt% to about 90wt%, and even more preferably from about 40wt% to about 85wt% of the styrene-containing copolymer, with the remainder being the rigid graft phase.

The rigid graft phase comprises a copolymer formed from a styrene monomer composition together with an unsaturated monomer comprising a nitrile group. As used herein, "styrene monomer" includes monomers of formula (9) wherein each X ^c is independently hydrogen, C ₁-C₄ alkyl, phenyl, C ₇-C₉ aralkyl, C ₇-C₉ alkaryl, C ₁-C₄ alkoxy, phenoxy, chloro, bromo, or hydroxy, and R is hydrogen, C ₁-C₂ alkyl, bromo, or chloro. Specific examples are styrene, 3-methylstyrene, 3, 5-diethylstyrene, 4-n-propylstyrene, alpha-methylstyrene, alpha-methylvinyltoluene, alpha-chlorostyrene, alpha-bromostyrene, dichlorostyrene, dibromostyrene, tetrachlorostyrene, etc. Combinations comprising at least one of the foregoing styrenic monomers may be used.

Further as used herein, unsaturated monomers comprising a nitrile group include monomers of formula (10) wherein R is hydrogen, C ₁-C₅ alkyl, bromine, or chlorine, and X ^c is cyano. Specific examples include acrylonitrile, ethacrylonitrile, methacrylonitrile, α -chloroacrylonitrile, β -chloroacrylonitrile, α -bromoacrylonitrile, and the like. Combinations comprising at least one of the foregoing monomers may be used.

The rigid graft phase of the styrene-containing copolymer may further optionally contain other monomers copolymerizable therewith, including other monovinylaromatic monomers and/or monovinylic monomers such as itaconic acid, acrylamide, N-substituted acrylamide or methacrylamide, maleic anhydride, maleimide, N-alkyl-, aryl-, or haloaryl-substituted maleimide, glycidyl (meth) acrylates, and monomers of the formula (10). Specific comonomers include C ₁-C₄ alkyl (meth) acrylates, such as methyl methacrylate.

The rigid copolymer phase generally comprises from about 10 to about 99wt%, preferably from about 40 to about 95wt%, more preferably from about 50 to about 90wt%, from about 1 to about 90wt%, preferably from about 10 to about 80wt%, more preferably from about 10 to about 50wt%, of an unsaturated monomer comprising a nitrile group, and from 0 to about 25wt%, preferably from 1 to about 15wt%, of other comonomers, each based on the total weight of the rigid copolymer phase.

The styrene-containing copolymer may further comprise a separate matrix or continuous phase of ungrafted rigid copolymer that may be obtained simultaneously with the styrene-containing copolymer. The styrene-containing copolymer may comprise about 40 to about 95 weight percent of the elastomer-modified graft copolymer and about 5 to about 65 weight percent of the rigid copolymer, based on the total weight of the styrene-containing copolymer. In another aspect, the styrene-containing copolymer may comprise from about 50 to about 85wt%, more preferably from about 75 to about 85wt%, of the elastomer-modified graft copolymer, along with from about 15 to about 50wt%, more preferably from about 15 to about 25wt%, of the rigid copolymer, based on the total weight of the styrene-containing copolymer.

Various bulk polymerization processes for styrene-containing copolymer resins are known. In the multi-zone plug flow bulk process, a series of polymerization vessels (or columns) connected to each other in series provide a plurality of reaction zones. The elastomeric butadiene may be dissolved in one or more monomers used to form the rigid phase and the elastomeric solution fed to the reaction system. The elastomer is grafted with a rigid copolymer (e.g., SAN) during a reaction that may be thermally or chemically initiated. Bulk copolymers (also known as free copolymers, matrix copolymers or non-grafted copolymers) are also formed within the continuous phase comprising the dissolved rubber. As polymerization continues, domains of free copolymer form in the continuous phase of the rubber/comonomer to provide a two-phase system. As the polymerization proceeds and more free copolymer is formed, the elastomer-modified copolymer begins to disperse itself as particles in the free copolymer and the free copolymer becomes the continuous phase (phase inversion). Some free copolymer is also typically enclosed in the elastomer-modified copolymer phase. After phase inversion, additional heating may be used to complete the polymerization. Many modifications of this basic process have been described, for example, in U.S. Pat. No. 3,511,895, which describes a continuous bulk ABS process that provides controlled molecular weight distribution and microgel particle size using a three-stage reactor system. In the first reactor, the elastomer/monomer solution is charged to the reaction mixture with high agitation to uniformly precipitate discrete rubber particles throughout the reactor body before appreciable crosslinking can occur. The solids content of the first, second and third reactors are carefully controlled so that the molecular weight falls within the desired range. U.S. patent No. 3,981,944 discloses the use of styrene monomer to dissolve/disperse elastomer particles to extract the elastomer particles prior to the addition of unsaturated monomers including nitrile groups and any other comonomers. U.S. patent No. 5,414,045 discloses reacting a liquid feed composition comprising a styrene monomer composition, an unsaturated nitrile monomer composition, and an elastomeric butadiene polymer in a plug flow grafting reactor to a point prior to phase inversion and reacting a first polymerization product therefrom (grafted elastomer) in a continuously stirred tank reactor to produce a phase inverted second polymerization product, which can then be further reacted in a finishing reactor and then devolatilized to produce the desired final product.

The linear homopolycarbonate or linear homopolycarbonate and the styrene-containing copolymer may be present in an amount of about 10 to about 99 weight percent, based on the total weight of the polycarbonate composition. Within this range, the linear homopolycarbonate or combination of linear homopolycarbonate and styrene-containing copolymer may be present in an amount of about 50 to about 99wt%, or about 60 to about 95wt%, or about 65 to about 95wt%, or about 70 to about 95 wt%.

In addition to the linear homopolycarbonate or the combination of linear homopolycarbonate and styrene-containing copolymer, a poly (carbonate-siloxane) comprising a siloxane content of about 10 to less than about 30wt% is present in the polycarbonate composition. As used herein, the "siloxane content" of a poly (carbonate-siloxane) refers to the content of siloxane units based on the total weight of the polycarbonate composition. Within this range, the poly (carbonate-siloxane) copolymer may have a siloxane content of about 15wt% to about 25 wt%.

The polysiloxane block of the poly (carbonate-siloxane) comprises repeating diorganosiloxane units in formula (10)

Wherein each R is independently a C _1-13 monovalent organic group. For example, R may be C _1-13 alkyl, C _1-13 alkoxy, C _2-13 C alkenyl, C _2-13 alkenyloxy, C _3-6 cycloalkyl, C _3-6 cycloalkoxy, C _6-14 aryl, C _6-10 aryloxy, C _7-13 arylalkylene, C _7-13 arylalkyleneoxy, C _7-13 alkylarylene, or C _7-13 alkylaryleneoxy. The above groups may be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. In one aspect, when a transparent poly (carbonate-siloxane) is desired, R is not substituted with halogen. Combinations of the foregoing R groups may be used in the same copolymer. The polysiloxane blocks of the poly (carbonate-siloxane) may be substantially free of or exclude hydride-functionalized siloxane repeating units. Referring to formula (10), the hydride-functionalized siloxane repeating unit has a hydrogen in at least one position corresponding to R. "substantially free of hydride-functional siloxane repeating units" as used herein refers to less than 1wt%, less than 0.1wt%, or less than 0.01wt% of hydride-functional siloxane repeating units, based on the total weight of the poly (carbonate-siloxane).

The value of E in formula (10) can vary widely depending on the type and relative amounts of the components in the polycarbonate composition, the desired properties of the composition, and the like. Typically, E has an average value of 2 to 1,000, preferably 2 to 500, 2 to 200, or 2 to 125, 5 to 80, or 10 to 70. In one aspect, E has an average value of 10 to 80 or 10 to 40, and in yet another aspect, E has an average value of 40 to 80, or 40 to 70. Where E has a lower value, for example less than 40, it may be desirable to use a relatively larger amount of poly (carbonate-siloxane) copolymer. Conversely, where E has a higher value, e.g., greater than 40, a relatively lower amount of poly (carbonate-siloxane) copolymer may be used. A combination of first and second (or more) poly (carbonate-siloxane) copolymers may be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.

In one aspect, the polysiloxane block has formula (11):

wherein E and R are as defined for formula (10), each R may be the same or different and is as defined above, and Ar may be the same or different and is a substituted or unsubstituted C _6-30 arylene group, wherein the bond is directly attached to the aromatic moiety. The Ar group in formula (11) may be derived from a C _6-30 dihydroxyarylene compound, such as a dihydroxyarylene compound of formula (3) or (6). The dihydroxyarylene compound is 1, 1-bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, 1-bis (4-hydroxyphenyl) propane 1, 1-bis (4-hydroxyphenyl) n-butane, 2-bis (4-hydroxy-1-methylphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl sulfide), and 1, 1-bis (4-hydroxy-tert-butylphenyl) propane.

In another aspect, the polysiloxane block has formula (13):

Wherein R and E are as described above, and each R ⁵ is independently a divalent C _1-30 organic group, and wherein the polymerized polysiloxane units are the reaction residues of their corresponding dihydroxy compounds. In a particular aspect, the polysiloxane block is of formula (14):

Wherein R and E are as defined above. R ⁶ in formula (14) is a divalent C _2-8 aliphatic group. Each M in formula (14) may be the same or different and may be halogen, cyano, nitro, C _1-8 alkylthio, C _1-8 alkyl, C _1-8 alkoxy, C _2-8 alkenyl, C _2-8 alkenyloxy, C _3-8 cycloalkyl, C _3-8 cycloalkoxy, C _6-10 aryl, C _6-10 aryloxy, C _7-12 aralkyl, C _7-12 aralkoxy, C _7-12 alkylaryl, or C _7-12 alkylaryl, wherein each n is independently 0,1, 2,3, or 4.

In one aspect, M is bromo or chloro, an alkyl group such as methyl, ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy, or an aryl group such as phenyl, chlorophenyl, or tolyl, R ⁶ is dimethylene, trimethylene, or tetramethylene, and R is C _1-8 alkyl, a haloalkyl group such as trifluoropropyl, cyanoalkyl, or an aryl group such as phenyl, chlorophenyl, or tolyl. In another aspect, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In yet another aspect, R is methyl, M is methoxy, n is 1, and R ⁶ is a divalent C _1-3 aliphatic radical. Specific polysiloxane blocks are of the formula:

or combinations thereof, wherein E has an average value of 2 to 200, 2 to 125, 5 to 100, 5 to 50, 20 to 80, or 5 to 20.

The blocks of formula (14) may be derived from the corresponding dihydroxypolysiloxanes, which in turn may be prepared to effect platinum-catalyzed addition between siloxane hydrides and aliphatic unsaturated monophenols such as eugenol, 2-alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-t-butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4, 6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol and 2-allyl-4, 6-dimethylphenol. Poly (carbonate-siloxane) copolymers can then be prepared, for example, by the synthetic procedure of Hoover, european patent application publication No. 0524731A1, page 5, preparation 2.

The transparent poly (carbonate-siloxane) copolymer comprises carbonate units (1) derived from bisphenol a, and repeating siloxane units (14 a), (14 b), (14 c), or a combination thereof (preferably formula 14 a), wherein E has an average value of 4 to 50, 4 to 15, preferably 5 to 15, more preferably 6 to 15, and still more preferably 7 to 10. Transparent copolymers may be made using one or both of the tubular reactor processes described in U.S. patent application No. 2004/0039145A1, or poly (carbonate-siloxane) copolymers may be synthesized using the process described in U.S. patent No. 6,723,864.

In one aspect, a blend of bisphenol a homopolycarbonate and a poly (carbonate-siloxane) block copolymer of bisphenol a blocks and eugenol-terminated polydimethylsiloxane blocks is used, particularly:

Wherein x is 1 to 200, preferably 5 to 85, preferably 10 to 70, preferably 15 to 65, and more preferably 40 to 60, x is 1 to 500, or 10 to 200, and z is 1 to 1000, or 10 to 800. In one aspect, x is 1 to 200, y is 1 to 90 and z is 1 to 600, and in another aspect, x is 30 to 50, y is 10 to 30 and z is 45 to 600. The polysiloxane blocks can be randomly distributed or controlled distributed in the polycarbonate blocks.

In one aspect, the polycarbonate composition can comprise a poly (carbonate-siloxane) comprising a siloxane content of less than about 10wt% polysiloxane, preferably less than about 6wt%, and more preferably less than about 4wt%, based on the total weight of the poly (carbonate-siloxane) copolymer. In some aspects, the polycarbonate composition may exclude poly (carbonate-siloxane) comprising a siloxane content of less than 10 wt%.

The poly (carbonate-siloxane) may have a weight average molecular weight of 2,000 to 100,000 grams per mole (g/mol), preferably 5,000 to 50,000g/mol, as measured by gel permeation chromatography and using a crosslinked styrene-divinylbenzene column to sample concentrations of 1 mg/ml, as measured in accordance with polystyrene standards and calculated for polycarbonate. In some aspects, the poly (carbonate-siloxane) having a siloxane content of 30 to 70wt% and the poly (carbonate-siloxane) having a siloxane content of 10 to less than 30wt% may each have a weight average molecular weight of at least 25,000g/mol, preferably 27,000 g/mol. Within this range, the poly (carbonate-siloxane) may have a weight average molecular weight of 25,000g/mol to 100,000 g/mol. The poly (carbonate-siloxane) having a siloxane content of 30 to 70wt% preferably can have a weight average molecular weight of greater than 21,000g/mol, more preferably greater than 25,000 g/mol. When the weight average molecular weight of the poly (carbonate-siloxane) having a siloxane content of 30 to 70wt% is within these ranges, delamination of the molded sample can be avoided. The poly (carbonate-siloxane) having a siloxane content of 30 to 70wt% can have a weight average molecular weight of greater than 30,000 to less than 50,000 g/mol. When the weight average molecular weight of the poly (carbonate-siloxane) having a siloxane content of 30 to 70wt% is within this range, the processability and chemical resistance can be improved.

The poly (carbonate-siloxane) having a siloxane content of 10wt% to less than 30wt% can have a weight average molecular weight of 25,000g/mol to 40,000g/mol, more preferably 27,000g/mol to 32,000g/mol, as measured by gel permeation chromatography using a crosslinked styrene-divinylbenzene column in accordance with polystyrene standards at a sample concentration of 1mg/ml and calculated for polycarbonate.

In one aspect, the composition comprises less than or equal to about 5wt% or less than or equal to about 1wt%, or less than or equal to about 0.1wt% of a poly (carbonate-siloxane) comprising a siloxane content of less than about 10 wt%. Poly (carbonate-siloxane) including a siloxane content of less than about 10wt% can be excluded from the composition. Preferably, poly (carbonate-siloxane) comprising a siloxane content of about 6wt% can be excluded from the composition.

The poly (carbonate-siloxane) having a siloxane content of about 10 to less than about 30wt% based on the total weight of the polycarbonate composition can be present in an amount effective to provide about 1 to about 6wt%, or about 3 to about 6wt% of the siloxane.

The poly (carbonate-siloxane) may have a melt volume flow rate of 1 to 50 cubic centimeters per 10 minutes (cc/10 min), preferably 2 to 30cc/10min, measured at 300 ℃ per 1.2 kg. Combinations of poly (carbonate-siloxanes) with different flow properties may be used to achieve the overall desired flow properties.

The polycarbonate composition comprises Ultra High Molecular Weight (UHMW) polydimethylsiloxane. In some aspects, one or more of the two methyl groups on each siloxane repeating unit can be substituted with other functional groups to affect compatibility within a given composition.

The number of repeating units in UHMW polydimethylsiloxanes can be up to several thousand, which can be up to a million g/mol molecular weight. The UMHW polydimethylsiloxane can have a weight average molecular weight of at least 100,000g/mol or at least 120,000g/mol according to GPC methods using polystyrene standards. UMHW polydimethyl siloxane can be included as a Masterbatch (MB) in the carrier resin. The carrier resin is not particularly limited and may include any thermoplastic polymer as long as the thermoplastic polymer is compatible with the polycarbonate composition. In some aspects, the carrier resin is a polycarbonate. UMHW polydimethylsiloxane as MB in polycarbonate (30 wt%) was available as PEARLENE, MB01 from Momentive Performance Materials.

The UHMW polydimethylsiloxane is present in an amount effective to provide a siloxane content of from greater than about 0.3 to less than about 0.9wt%, or from greater than about 0.3 to less than about 0.75wt%, each based on the total weight of the polycarbonate composition. Aesthetic problems such as gate blushing and surface defects can occur when the amount of UHMW polydimethylsiloxane exceeds an amount effective to provide a silicone content of about 0.9 weight percent.

The composition provided by the poly (carbonate-siloxane) having a siloxane content of about 10wt% to less than about 30wt% has a siloxane content greater than the siloxane content provided by the UHMW polydimethylsiloxane. The weight ratio of silicone provided by poly (carbonate-silicone) having a silicone content of from about 10wt% to less than about 30wt% to silicone provided by UHMW polydimethylsiloxane may be greater than about 1:1, or at least about 2:1, or at least about 3:1, or at least about 4:1, or at least about 5:1.

The polycarbonate composition comprises a flame retardant. The flame retardant may comprise a halogenated flame retardant provided that the halogen content of the composition is within the guidelines as set forth in IEC 61249-2-21 and/or UL 746H. According to both IEC 61249-2-21 and UL 746H, the bromine and chlorine contents are each 900ppm or less and the total bromine, chlorine and fluorine content of the polycarbonate composition is 1500ppm or less. UL 746H has the additional requirement that the fluorine content of the composition be below 900 ppm. These values may be calculated or determined by elemental analysis techniques.

Halogenated flame retardants may include halogenated compounds and polymers of formula (20):

Wherein R is an alkylene, alkylidene, or cycloaliphatic linkage (e.g., methylene, ethylene, propylene, isopropylidene, butylene, isobutylene, pentylene, cyclohexylidene, cyclopentylidene, and the like), a linkage selected from the group consisting of an oxygen ether, a carbonyl, an amine, a sulfur-containing linkage (e.g., sulfide, sulfoxide, or sulfone), a phosphorus-containing linkage, and the like, or R may also consist of two or more alkylene or alkylidene linkages connected by a group such as aromatic, amino, ether, carbonyl, sulfide, sulfoxide, sulfone, phosphorus-containing linkage, and the like; ar and Ar' may be the same or different and are aromatic groups of mono-or poly-carbocycle, such as phenylene, biphenylene, terphenylene, naphthylene, etc., Y is an organic, inorganic or organometallic group, such as halogen (e.g., chlorine, bromine, iodine, or fluorine), an ether group of the general formula OE, wherein E is a monovalent hydrocarbon group similar to X, a monovalent hydrocarbon group of the type represented by R, or other substituents (e.g., nitro, cyano, etc.), the substituents being substantially inert, provided that at least one and preferably two halogen atoms are present per aryl nucleus, each X is the same or different and is a monovalent hydrocarbon group, such as alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, decyl, etc.), aryl ((e.g., phenyl, naphthyl, biphenyl, xylyl, tolyl, etc.), arylalkylene (e.g., benzyl, vinylphenyl, etc.), alicyclic (e.g., cyclopentyl, cyclohexyl, etc.), and monovalent hydrocarbon groups containing inert substituents therein, the letter d representing an integer of 1 to a maximum equal to the number of replaceable hydrogens substituted on the aromatic ring comprising Ar or Ar ', the letter e representing an integer from 0 to a maximum equal to the number of replaceable hydrogens on R, the letters a, b and c representing integers comprising 0, provided that neither a nor c can be 0, or a or c can be 0, or that when b is 0, the aromatic groups are linked by a direct carbon-carbon bond, the hydroxyl groups on the aromatic groups and Y substituents, ar and Ar' can vary in ortho, meta or para positions to the aromatic ring, and the groups can be in any possible geometric relationship with each other.

Included within the scope of the above formula are representative bisphenols of2, 2-bis- (3, 5-dichlorophenyl) -propane; bis- (2-chlorophenyl) -methane; bis (2, 6-dibromophenyl) -methane; 1, 1-bis- (4-iodophenyl) -ethane, 1, 2-bis- (2, 6-dichlorophenyl) -ethane, 1-bis- (2-chloro-4-iodophenyl) -ethane, 1-bis- (2-chloro-4-methylphenyl) -ethane, 1-bis- (3, 5-dichlorophenyl) -ethane, 2-bis- (3-phenyl-4-bromophenyl) -ethane, 2, 6-bis- (4, 6-dichlorophenyl) -propane, 2-bis- (2, 6-dichlorophenyl) -pentane, 2-bis- (3, 5-dibromophenyl) -hexane, bis- (4-chlorophenyl) -phenyl-methane, bis- (3, 5-dichlorophenyl) -cyclohexylmethane, bis- (3-nitro-4-bromophenyl) -methane, bis- (4-hydroxy-2, 6-dichloro-3-methoxyphenyl) -methane, and 2, 2-bis- (3, 5-dichloro-4-hydroxyphenyl) -propane, 2-bis- (3-bromo-4-hydroxyphenyl) -methane Propane. Also included within the above formulas are 1, 3-dichlorobenzene, 1, 4-dibromobenzene, 1, 3-dichloro-4-hydroxyphenyl, and biphenyls such as 2,2' -dichlorobenzene, polybrominated 1, 4-diphenoxybenzene, 2,4' -dibromobiphenyl, and 2,4' -dichlorobenzene, decabromodiphenyl ether, and the like.

Oligomeric and polymeric halogenated aromatic compounds are also useful, such as copolycarbonates of bisphenol a and tetrabromobisphenol a with carbonate precursors (e.g., phosgene). Metal synergists, such as antimony oxide, may also be used with the flame retardant.

Inorganic flame retardants may also be used, for example salts of C _2-16 alkyl sulfonates such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluorooctane sulfonate and tetraethylammonium perfluorohexane sulfonate, salts of aromatic sulfonates such as sodium benzenesulfonate, sodium toluenesulfonate (NATS) and the like, salts of aromatic sulfone sulfonates such as potassium diphenylsulfone sulfonate (KSS) and the like, salts formed by reaction, for example, alkali or alkaline earth metals (e.g., lithium, sodium, potassium, magnesium, calcium and barium salts) and inorganic acid double salts, for example, oxo-anions (e.g., alkali and alkaline earth metal salts of carbonic acid such as Na ₂CO₃、K₂CO₃、MgCO₃、CaCO₃, and BaCO ₃, or fluoro-anion complexes such as Li₃AlF₆、BaSiF₆、KBF₄、K₃AlF₆、KAlF₄、K₂SiF₆、 or Na ₃AlF₆ and the like). Rimar salts and KSS and NATS, alone or in combination with other flame retardants, are particularly useful. Rimar salts and KSS and NATS, alone or in combination with other flame retardants, are particularly useful.

Di-or polyfunctional aromatic phosphorus-containing compounds are also useful, for example, compounds of formula (14):

wherein each G ² is independently a hydrocarbyl or hydrocarbyloxy group having from 1 to 30 carbon atoms, and n is from 0 to 3.

Specific aromatic organophosphorus compounds have two or more phosphorus-containing groups and include acid esters of formula (15):

Wherein R ¹⁶、R¹⁷、R¹⁸, and R ¹⁹ are each independently C _1-8 alkyl, C _5-6 cycloalkyl, C _6-20 aryl, Or C _7-12 arylalkylene, each optionally substituted with C _1-12 alkyl, Preferably C _1-4 alkyl, and X is a mono-or polynuclear aromatic C _6-30 moiety or a straight or branched C _2-30 aliphatic group which may be OH-substituted and may contain up to 8 ether linkages, provided that R ¹⁶、R¹⁷、R¹⁸、R¹⁹, and at least one of X is an aromatic group. In some aspects, R ¹⁶、R¹⁷、R¹⁸, and R ¹⁹ are each independently C _1-4 alkyl, naphthyl, phenyl (C _1-4) alkylene, Or an aryl group optionally substituted with a C _1-4 alkyl group. specific aryl moieties are tolyl, phenyl, xylyl, propylphenyl, or butylphenyl. In some aspects, X in formula (15) is a mononuclear or polynuclear aromatic C _6-30 moiety derived from diphenols. Further, in formula (15), n is each independently 0 or 1, and in some aspects n is equal to 1. Also in formula (15), q is 0.5 to 30, 0.8 to 15, 1 to 5, or 1 to 2. Preferably, X may be represented by the following divalent group (16) or a combination thereof.

In these aspects, each of R ¹⁶、R¹⁷、R¹⁸, and R ¹⁹ may be aromatic, i.e., phenyl, n is 1, and p is 1-5, preferably 1-2. In some aspects, at least one of R ¹⁶、R¹⁷、R¹⁸、R¹⁹, and X corresponds to a monomer used to form a polycarbonate, e.g., bisphenol a or resorcinol. In another aspect, X is derived from resorcinol, hydroquinone, bisphenol A, or diphenylphenol, among others, and R ¹⁶、R¹⁷、R¹⁸、R¹⁹ is aromatic, preferably phenyl. A specific aromatic organophosphorus compound of this type is resorcinol bis (diphenyl phosphate), also known as RDP. Another specific class of aromatic organophosphorus compounds having two or more phosphorus-containing groups are compounds of formula (17)

Wherein R ¹⁶、R¹⁷、R¹⁸、R¹⁹, n and q are as defined for formula (19), and wherein Z is C _1-7 alkylidene, C _1-7 alkylene C _5-12 cycloalkylidene, -O-, -S-, -SO ₂ -, or-CO-, isopropylidene is preferred. A specific aromatic organophosphorus compound of this type is bisphenol a bis (diphenyl phosphate), also known as BPADP, where R ¹⁶、R¹⁷、R¹⁸, and R ¹⁹ are each phenyl, each n is 1, and q is from 1 to 5, from 1 to 2, or 1.

Flame retardant compounds containing phosphorus-nitrogen bonds include phosphazenes, phosphonitriles chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris (aziridinyl) phosphine oxide. Specific examples include phosphoramides of the formula:

Wherein each A moiety is a2, 6-dimethylphenyl moiety or a2, 4, 6-trimethylphenyl moiety. These phosphoramides are piperazine type phosphoramides.

Phosphazenes (18) and cyclophosphazenes (19)

In particular, use may be made of wherein w1 is 3 to 10,000 and w2 is 3 to 25, preferably 3 to 7, and each R ^w is independently a C _1-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene group. In the above groups, at least one hydrogen atom of these groups may be substituted with a group having N, S, O or an F atom, or an amino group. For example, each R ^w may be a substituted or unsubstituted phenoxy, amino, or polyoxyalkylene group. Any given R ^w may further be cross-linking to another phosphazene group. Exemplary crosslinks include bisphenol groups, such as bisphenol a groups. Examples include phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaphenoxycyclopentaphosphazene, and the like. Combinations of different phosphazenes may be used. A number of phosphazenes and their synthesis are described in H.R. Allcook, "Phosphorous-Nitrogen Compounds" ACADEMIC PRESS (1972). In an aromatic organophosphorus compound having at least one organic aromatic group, the aromatic group may be a substituted or unsubstituted C _3-30 group, the C _3-30 group containing one or more monocyclic or polycyclic aromatic moieties, which may optionally contain up to three heteroatoms (N, O, P, S, or Si), and optionally further containing one or more non-aromatic moieties, such as alkyl, alkenyl, alkynyl, or cycloalkyl. The aromatic moiety of the aromatic group may be bonded directly to the phosphorus-containing group or via another moiety (e.g., an alkylene group). The aromatic moiety of the aromatic group may be bonded directly to the phosphorus-containing group or via another moiety (e.g., an alkylene group). In one aspect, the aromatic groups are the same as the aromatic groups of the polycarbonate backbone, such as bisphenol groups (e.g., bisphenol a), shan Yafang-based groups (e.g., 1, 3-phenylene or 1, 4-phenylene), or a combination comprising at least one of the foregoing.

The phosphorus-containing groups may be phosphate (P (=o) (OR) ₃), phosphite (P (OR) ₃), phosphonate (RP (=o) (OR) ₂), phosphinate (R ₂ P (=o) (OR)), phosphine oxide (R ₃ P (=o)), OR phosphine (R ₃ P), wherein each R of the foregoing phosphorus-containing groups may be the same OR different, provided that at least one R is an aromatic group. Combinations of different phosphorus-containing groups may be used. The aromatic group may be directly or indirectly bonded to phosphorus, or to oxygen of a phosphorus-containing group (i.e., an ester).

In aspects, the aromatic organophosphorus compound is a monomeric phosphate. Representative monomeric aromatic phosphate esters have the formula (GO) ₃ p=o, wherein each G is independently an alkyl, cycloalkyl, aryl, alkylarylene, or arylalkylene group having up to 30 carbon atoms, provided that at least one G is an aromatic group. The two G groups may be linked together to provide a cyclic group. In some aspects, G corresponds to a monomer used to form a polycarbonate, e.g., resorcinol. Exemplary phosphates include phenyl bis (dodecyl) phosphate, phenyl bis (neopentyl) phosphate, phenyl bis (3, 5 '-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di (p-tolyl) phosphate, di (2-ethylhexyl) p-tolyl phosphate, trimethylphenyl phosphate, di (2-ethylhexyl) phenyl phosphate, tri (nonylphenyl) phosphate, di (dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis (2, 5' -trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and the like. Specific aromatic phosphates are those in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like.

Di-or polyfunctional aromatic organophosphorus compounds are also useful, for example, compounds of the formula:

Wherein each G ¹ is independently a C _1-30 hydrocarbyl group, each G ² is independently a C _1-30 hydrocarbyl or hydrocarbyloxy group, X ^a is as defined in formula (3) or formula (4), each X is independently bromine or chlorine, m is 0 to 4, and n is 1 to 30. In a particular aspect, X ^a is a single bond, methylene, isopropylidene or 3, 5-trimethylcyclohexylidene.

Specific aromatic organophosphorus compounds include acid esters of formula (9):

Wherein each R ¹⁶ is independently C _1-8 alkyl, C _5-6 cycloalkyl, C _6-20 aryl, Or C _7-12 arylalkylene, each optionally substituted with C _1-12 alkyl, specifically C _1-4 alkyl, and X is a mono-or polynuclear aromatic C _6-30 moiety or a linear or branched C _2-30 aliphatic group, which may be OH-substituted and may contain up to 8 ether linkages, provided that at least one R ¹⁶ or X is an aromatic group, each n is independently 0 or 1, and q is from 0.5 to 30. In some aspects, each R ¹⁶ is independently C _1-4 alkyl, naphthyl, phenyl (C _1-4) alkylene, an aryl group optionally substituted with C _1-4 alkyl, each X is a mono-or polynuclear aromatic C _6-30 moiety, each n is 1, and q is from 0.5 to 30. In some aspects, each R ¹⁶ is aromatic, such as phenyl, each X is a mono-or polynuclear aromatic C _6-30 moiety, including moieties derived from formula (2), n is 1, and q is from 0.8 to 15. In other aspects, each R ¹⁶ is phenyl, X is tolyl, xylyl, propylphenyl, or butylphenyl, one of the following divalent groups

Or a combination comprising one or more of the foregoing, n is 1, and q is 1 to 5, or 1 to 2. In some aspects, at least one R ¹⁶ or X corresponds to a monomer used to form a polycarbonate, e.g., bisphenol a, resorcinol, etc. Aromatic organophosphorus compounds of this type include bis (diphenyl) phosphate of hydroquinone, resorcinol bis (diphenyl phosphate) (RDP), and bisphenol a bis (diphenyl) phosphate (BPADP), as well as their oligomeric and polymeric counterparts.

The organophosphorus flame retardant containing a phosphorus-nitrogen bond may be a phosphazene, a phosphazene chloride, a phosphazene amide, a phosphoric acid amide, a phosphonic acid amide, a phosphinic acid amide, or a tris (aziridinyl) phosphine oxide. These flame retardant additives are commercially available. In one aspect, the organophosphorus flame retardant containing a phosphorus-nitrogen bond is a phosphazene or cyclic phosphazene of the formula:

Wherein w1 is 3 to 10,000, w2 is 3 to 25, or 3 to 7, and each R ^w is independently a C _1-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene group. In the above groups, at least one hydrogen atom of these groups may be substituted with a group having N, S, O or an F atom, or an amino group. For example, each R ^w may be a substituted or unsubstituted phenoxy, amino, or polyoxyalkylene group. Any given R ^w may further be cross-linking to another phosphazene group. Exemplary crosslinks include bisphenol groups, such as bisphenol a groups. Examples include phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaphenoxycyclopentaphosphazene, and the like. In one aspect, the phosphazene has a structure represented by the following formula:

Commercially available phenoxyphosphazenes having the above-described structure are LY202 manufactured and sold by LANYIN CHEMICAL co., ltd., FP-110 manufactured and sold by Fushimi Pharmaceutical co., ltd., and SPB-100 manufactured and sold by Otsuka Chemical co., ltd.

When present, the phosphorus-containing flame retardant is typically present in an amount effective to provide up to 5wt% phosphorus, based on the total weight of the composition. Further, if halogenated, the phosphorus-containing flame retardant is typically present in an amount effective to provide less than about 900ppm each of bromine, chlorine, and optionally fluorine, and less than about 1500ppm total halogen content (e.g., bromine, chlorine, and fluorine), based on the total weight of the composition.

Additive compositions may be used that include one or more additives selected to achieve desired properties, provided that the additives are also selected so as not to significantly adversely affect the flame retardancy and anti-drip properties of the polycarbonate composition. The additive composition or the individual additives may be mixed at a suitable time during the mixing of the components used to form the composition. The additives may be soluble or insoluble in the polycarbonate. The additive composition may include an impact modifier, a flow modifier, a filler (e.g., particles, polytetrafluoroethylene (PTFE), glass, carbon, minerals, or metals), a reinforcing agent (e.g., glass fibers), an antioxidant, a heat stabilizer, a light stabilizer, an Ultraviolet (UV) light stabilizer, a UV absorbing additive, a plasticizer, a lubricant, a mold release agent (e.g., a mold release agent), an antistatic agent, an antifogging agent, an antimicrobial agent, a colorant (e.g., a dye or pigment), a surface effect additive, a radiation stabilizer, or a combination thereof. In some aspects, the additive composition may not include a filler, such as a mineral filler. For example, a combination of a heat stabilizer, a mold release agent, and an ultraviolet light stabilizer may be used. Typically, the additives are used in amounts generally known to be effective. For example, the total amount of additive composition (other than any impact modifier, filler, or reinforcing agent) may be 0.001 to 10.0wt%, or 0.01 to 5wt%, each based on the total weight of the polymer of the composition.

Colorants such as pigment or dye additives may also be present. Useful pigments can include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxide, iron oxide, and the like, sulfides such as zinc sulfide, and the like, aluminates, sodium thiosulfate sulfate, chromates, and the like, carbon black, zinc ferrite, ultramarine, organic pigments such as azo, diazo, quinacridone, perylene, naphthalene tetracarboxylic acid, flavanthrone, isoindolinone, tetrachloroisoindolinone, anthraquinone, anthrone, dioxazine, phthalocyanine, and azo lakes, pigment red 101, pigment red 122, pigment red 149, pigment red 177, pigment red 179, pigment red 202, pigment violet 29, pigment blue 15, pigment blue 60, pigment green 7, pigment yellow 119, pigment yellow 147, pigment yellow 150, and pigment brown 24, or combinations thereof.

The polycarbonate compositions can be prepared by various methods. For example, powdered polycarbonate, flame retardant, or other optional components are optionally first blended with filler in an hemschel-Mixer high speed Mixer. Other low shear methods, including but not limited to hand mixing, may also accomplish this blending. The blend is then fed through a hopper to the throat of a twin screw extruder. Alternatively, at least one component may be incorporated into the composition by feeding directly into the extruder through a side filler (sidestuffer) at the throat or downstream. The additives may also be mixed with the desired polymer into a masterbatch and fed to the extruder. The extruder is typically operated at a temperature above that necessary to cause the composition to flow. The extrudate was immediately quenched in a water bath and pelletized. The pellets so prepared may be one-quarter inch long or less, as desired. Such pellets may be used for subsequent molding, shaping, or shaping.

Flammability testing was performed according to the Underwriter laboratory bulletin 94 (Underwriter's Laboratory Bulletin 94) titled "flammability test of plastic materials for devices and parts in appliances" (ISBN 0-7629-0082-2), fifth edition, 29 th 1996, procedure through and including 12 th 2003 in combination with revisions. Several grades may be applied based on the burn rate, the extinguishing time, the resistance to dripping, and whether dripping is burning. According to this procedure, materials can be classified as UL-94HB, V-0, V-1, V-2, 5VA and/or 5VB.

Shaped, formed, or molded articles comprising the polycarbonate compositions are also provided. The polycarbonate compositions can be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming. Some embodiments of the article include computer and business machine housings, such as housings for monitors, hand-held electronic device housings, such as housings for cellular telephones, electrical connectors, and components of lighting fixtures, ornaments, home appliances, roofs, greenhouses, sun rooms, swimming pool covers, and the like. In some aspects, the polycarbonate compositions may be used in articles such as mobile phones, tablets, industrial housings, circuit protection, personal safety helmets, electric Vehicle Supply Equipment (EVSE) housings, and connectors. In some aspects, the polycarbonate compositions may be used in applications such as industry, construction, and architecture, automobile exteriors and interiors, electrical and electronic, sports/leisure, personal accessories, mass transportation, health care, and consumer. It is also suitable for defense, outdoor lawns and landscapes, water management, fossil, electrical devices and displays, special vehicles, surgery, ophthalmology, railways, home decoration, household appliances, electrical components and infrastructure, personal entertainment, healthcare, patient testing, under-hood automobiles, commercial appliances, industrial materials handling, aerospace, and the like.

The polycarbonate compositions are further illustrated by the following non-limiting examples.

Examples

The following components were used in the examples. The amount of each component is in wt% based on the total weight of the composition, unless specifically stated otherwise.

The materials shown in table 1 were used.

TABLE 1

Test samples were prepared as described below and the following test methods were used.

Typical compounding procedures are described below, where the various formulations are prepared by dry blending the raw materials directly and homogenized with a paint shaker prior to compounding. These formulations were compounded on a 26mm Coperion ZSK corotating twin-screw extruder. Typical extrudates are listed in table 2.

TABLE 2

Parameters (parameters)	Unit (B)	25mm ZSK
			Feed temperature	°C	177
Zone 1 temperature	°C	232
			Temperature in region 2-8	°C	266
Die temperature	°C	271
			Screw speed	rpm	400
Throughput of	kg/h	70
			Torque moment	%	75-80

The test parts were molded using a Demag molding machine for standard physical property testing. (see Table 3 for parameters).

TABLE 3 Table 3

Parameters (parameters)	Unit (B)
			Pre-drying time	h	4
Predrying temperature	°C	120
			Region 1-3 temperature	°C	290
Nozzle temperature	°C	290
			Mold temperature	°C	82
Screw speed	rpm	100
			Back pressure	Bar of	3.4
Injection time	s	1-2
			About cycle time	s	31-35

Sample preparation and testing methods are described in table 4. There is a need to add descriptions and tables for UL-94 flame testing.

TABLE 4 Table 4

The samples were subjected to flammability tests at 1.5mm, 1.0mm, and 0.8mm thicknesses according to Underwriter's Laboratory (UL) UL 94 standards. In some cases, the second set of 5 bars is tested to give an indication of the robustness of the rating. The present report uses the following definitions as shown in table 5. The total Flame Out Time (FOT) of all bars (fot=t1+t2) was determined. For each group of 10 bars, a V rating was obtained, 5 adjusted at 23 ℃ for 48 hours and 5 adjusted at 70 ℃ for 168 hours.

TABLE 5

Examples 1 to 8

Table 6 shows the compositions and properties of the following comparative examples and examples. The comparative examples are indicated by asterisks.

TABLE 6

Table 6 shows compositions comprising BPA homopolycarbonate (PC-1, PC-2) in combination with a poly (carbonate-siloxane) comprising a higher siloxane content (i.e., 40 wt%) and a poly (carbonate-siloxane) comprising a lower siloxane content (i.e., 20 wt%) and a flame retardant for preparing molded samples having a white color. TiO ₂ was chosen as the colorant because it is a challenge to produce a white molded sample with a UL-94 burn test rating of V-0 at 1.5 mm. Comparative example 1 contained an anti-drip agent (TSAN), and the anti-drip agent was excluded from the remaining compositions in table 6. Comparative examples 1 and 2 show that removal of the anti-drip agent resulted in adverse effects on UL-94 burn test rating (from V-1 to V-2), number of drips (from no drip to 3 at 23 ℃ and no drip to 4 at 70 ℃, some of which ignite cotton), and FOT (from 1 to 3). FOT is a measure of how much molded stick has a flame out time of greater than 10 s. No anti-drip agent was present in examples 3-8. In contrast, UHMW polydimethylsiloxane was added. The combination of UHMW polydimethyl siloxane (loading of 1wt%,0.3wt% siloxane content based on the total weight of the composition) failed to improve UL-94 flame test rating, drop count, or FOT. When the UHMW polydimethylsiloxane was increased to 2wt% and 3wt%, the desired combination of UL-94 flame test rating of V-0 at 1.5mm thickness, no dripping at 23 or 70 ℃, and FOT of 0s was obtained (see examples 5-8). Although example 5 has a higher siloxane content than comparative examples 1-4, UHMW polydimethyl siloxane (at loadings greater than 1wt%, corresponding to a siloxane content of greater than 0.3wt%, based on the total weight of the composition) is present instead of the total siloxane content (contributed by both UHMW polydimethyl siloxane and poly (carbonate-siloxane)) that provides the desired combination of properties. Indeed, as demonstrated by comparative example 2 and examples 6 and 8, wherein no anti-drip agent was present, the desired combination of properties was not obtained when UHMW polydimethylsiloxane was not present even when the siloxane content of the total composition was the same (i.e., 4.44 wt%). Example 7 shows that increasing the total siloxane content to 5.34wt% also provides a combination of desirable properties.

The present invention further encompasses the following aspects.

Aspect 1. A polycarbonate composition comprising a linear homopolycarbonate and optionally a styrene-containing copolymer, a poly (carbonate-siloxane) comprising a siloxane content of about 10wt% to less than about 30wt%, present in an amount effective to provide a siloxane content of about 1wt% to about 6wt%, based on the total weight of the poly (carbonate-siloxane), an ultra-high molecular weight polydimethylsiloxane present in an amount effective to provide a siloxane of greater than about 0.3wt% to less than about 0.9wt%, based on the total weight of the composition, wherein the polydimethylsiloxane has a weight average molecular weight of at least 100,000 g/mole as determined by gel permeation chromatography based on polystyrene standards, a flame retardant, and optionally an additive composition, wherein the linear homopolycarbonate, optionally the styrene-containing copolymer, the poly (carbonate-siloxane), the ultra-high molecular weight polydimethylsiloxane, the flame retardant, and optionally the additive composition total 100wt%.

Aspect 1a the polycarbonate composition of aspect 1, wherein the additive composition comprises up to about 10wt%, or up to about 5wt% of the polycarbonate composition.

Aspect 1b the polycarbonate composition according to any of the preceding aspects, comprising about 60 to about 95wt%, preferably about 65 to about 95wt%, more preferably about 70 to about 95wt% of a linear homopolycarbonate and optionally a styrene-containing copolymer.

The polycarbonate composition of any of the preceding aspects, wherein the additive composition comprises an impact modifier, a flow modifier, a filler, a reinforcing agent, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light absorbing additive, a plasticizer, a lubricant, a mold release agent, an antistatic agent, an anti-fog agent, an antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, or a combination thereof.

The polycarbonate composition of any of the preceding aspects, wherein the additive composition comprises an impact modifier, a flow modifier, a reinforcing agent, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light absorbing additive, a plasticizer, a lubricant, a mold release agent, an antistatic agent, an anti-fog agent, an antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, or a combination thereof.

The polycarbonate composition of any of the preceding aspects, wherein the additive composition comprises an impact modifier, a flow modifier, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light absorbing additive, a plasticizer, a lubricant, a mold release agent, an antistatic agent, an anti-fog agent, an antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, or a combination thereof.

The polycarbonate composition of any of the preceding aspects, wherein the additive composition comprises a flow modifier, a reinforcing agent, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light absorbing additive, a plasticizer, a lubricant, a mold release agent, an antistatic agent, an antifogging agent, an antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, or a combination thereof.

The polycarbonate composition of any of the preceding aspects, wherein the calculated weight percent of the bromine and chlorine content of the polycarbonate composition is about 900ppm or less and the calculated weight percent of the total halogen content of the polycarbonate composition is about 1500ppm or less, or the calculated weight percent of the bromine, chlorine, and fluorine content of the polycarbonate composition is about 900ppm or less and the calculated weight percent of the total bromine, chlorine, and fluorine content of the polycarbonate composition is about 1500ppm or less.

Aspect 3. The polycarbonate composition according to aspect 1, wherein the molded sample comprising the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of less than 1.5 millimeters.

Aspect 4 the polycarbonate composition of any of the preceding aspects, wherein the poly (carbonate-siloxane) comprises repeating diorganosiloxane units of formula (10)

Wherein each R is independently a C _1-13 monovalent organic group, preferably C _1-13 alkyl, C _1-13 alkoxy, C _2-13 alkenyl, C _2-13 alkenyloxy, C _3-6 cycloalkyl, C _3-6 cycloalkoxy, C _6-14 aryl, C _6-10 aryloxy, C _7-13 arylalkylene, C _7-13 arylalkyleneoxy, C _7-13 alkylarylene, or C _7-13 alkylaryleneoxy, each optionally fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof.

Aspect 5. The polycarbonate composition of any of the preceding aspects, wherein the linear homopolycarbonate is a bisphenol a polycarbonate homopolymer comprising a linear bisphenol a polycarbonate homopolymer having a weight average molecular weight of 15,000 to 25,000g/mol, preferably 17,000 to 25,000g/mol, as determined by gel permeation chromatography according to polystyrene standards and calculated for polycarbonate, or a linear bisphenol a polycarbonate homopolymer having a weight average molecular weight of 26,000 to 40,000g/mol, preferably 27,000 to 35,000g/mol, as determined by gel permeation chromatography according to polystyrene standards and calculated for polycarbonate, or a combination thereof.

Aspect 6 the polycarbonate composition of any of the preceding aspects, wherein the poly (carbonate siloxane) comprises bisphenol a carbonate repeat units and poly (dimethylsiloxane) repeat units.

Aspect 7 the polycarbonate composition of any of the preceding aspects, wherein the poly (carbonate siloxane) has a siloxane content of about 15 to about 25 weight percent, based on the total weight of the poly (carbonate siloxane).

The polycarbonate composition of any of the preceding aspects, wherein the flame retardant comprises an alkyl sulfonate, an aromatic sulfonate, an organic phosphorus compound, or a combination thereof.

Aspect 9 the polycarbonate composition of any of the preceding aspects, wherein the flame retardant is non-halogenated.

Aspect 10 the polycarbonate composition of any of the preceding aspects, wherein a styrene-containing copolymer is present and comprises an elastomeric phase comprising (i) butadiene and having a glass transition temperature of less than 10 ℃, and (ii) a rigid polymer phase having a glass transition temperature of greater than 15 ℃ and comprising a copolymer of monovinylaromatic monomers comprising styrene and an unsaturated nitrile.

Aspect 11 the polycarbonate composition according to any of the preceding aspects, wherein the composition does not comprise a halogenated anti-drip agent, preferably a fluorinated anti-drip agent.

Aspect 12. The polycarbonate composition according to any of the preceding aspects, comprising a linear homopolycarbonate and optionally a styrene-containing copolymer, a poly (carbonate-siloxane) comprising a siloxane content of about 10wt% to less than about 30wt% of siloxane, present in an amount effective to provide a siloxane content of about 1wt% to about 6wt% based on the total weight of the polycarbonate composition, an ultra-high molecular weight polydimethylsiloxane present in an amount effective to provide a siloxane of greater than about 0.3wt% to less than about 0.9wt% based on the total weight of the composition, wherein the polydimethylsiloxane has a weight average molecular weight of at least 100,000 g/mole as determined by gel permeation chromatography according to polystyrene standards, and a flame retardant comprising an aromatic sulfonate, and optionally an additive composition.

Aspect 12a the polycarbonate composition of aspect 12, wherein the styrene-containing copolymer is present and comprises styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), styrene-acrylonitrile (SAN), or a combination thereof, preferably acrylonitrile-butadiene-styrene (ABS).

Aspect 13. A method of making the polycarbonate composition of any of the preceding aspects, the method comprising melt mixing the components of the composition.

Aspect 14. The method according to aspect 13, further comprising molding, casting or extruding the composition to provide the article.

Aspect 15 an article comprising the polycarbonate composition according to any of the preceding aspects.

Alternatively, the compositions, methods, and articles of manufacture may comprise, consist of, or consist essentially of any of the suitable materials, steps, or components disclosed herein. The compositions, methods, and articles of manufacture may additionally, or alternatively, be formulated so as to be free of, or substantially free of, any materials (or species), steps, or components that would otherwise be unnecessary to achieve the function or purpose of the compositions, methods, and articles of manufacture.

All ranges disclosed herein include endpoints, and endpoints can be combined independently of each other (e.g., the range of "up to 25wt%, or more specifically, 5wt% to 20wt%," includes the endpoints and all intermediate values of the range of "5wt% to 25wt%," etc.). In view of the measurements in question and the errors associated with the particular amounts of measurements (i.e., limitations of the measurement system), as used herein, "about" includes the stated values and means within the acceptable deviation of the particular values as determined by one of ordinary skill in the art. For example, "about" may mean within one or more standard deviations, or within ±30%, 20%, 10%, 5%, 1%, 0.5%, 0.2% or 0.1% of the value.

"Combination" includes blends, mixtures, alloys, reaction products, and the like. The terms "first," "second," and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms "a" and "an" and "the" do not denote a limitation of quantity, but rather are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Unless explicitly stated otherwise, "or" means "and/or". Reference throughout the specification to "some embodiments," "an embodiment," and so forth, means that a particular element described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. Furthermore, it should be understood that the described elements may be combined in any suitable manner in various embodiments. "combinations thereof are open and include any combination that includes at least one of the listed components or properties, optionally together with similar or equivalent components or properties not listed.

Unless specified to the contrary herein, all test criteria are the latest criteria validated from the filing date of the present application or, if priority is required, the filing date of the earliest priority application for which the test criteria appear.

Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through the carbon of the carbonyl group.

The term "alkyl" refers to branched or straight chain, unsaturated aliphatic hydrocarbon groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, and n-hexyl and sec-hexyl. "alkenyl" refers to a straight or branched monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., vinyl (-hc=ch ₂)). "alkoxy" refers to an alkyl group (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butoxy, linked via an oxygen. "alkylene" refers to a straight or branched, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH ₂ -) or propylene (-CH ₂)₃ -)). "cycloalkylene" refers to a divalent cyclic alkylene group, -C _nH_2n-x, where x is the number of hydrogens replaced with cyclizing. "cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, where all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "aryl" refers to an aromatic hydrocarbon group containing the indicated number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. "arylene" refers to a divalent aryl group. "Alkylenearylene" refers to an arylene group substituted with an alkyl group. "arylalkylene" refers to an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound that includes one or more of a fluoro, chloro, bromo, or iodo substituent. Combinations of different halogen groups (e.g., bromine and fluorine) or chlorine only groups may be present. The prefix "hetero" refers to a compound or group that includes at least one ring member of a heteroatom (e.g., 1,2, or 3 heteroatoms), where the heteroatoms are each independently N, O, S, si, or P. "substituted" means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituent(s) that may each independently be C _1-9 alkoxy, C _1-9 haloalkoxy, nitro (-NO ₂), nitro, Cyano (-CN), C _1-6 alkylsulfonyl (-S (=o) ₂ -alkyl), C _6-12 arylsulfonyl (-S (=o) ₂ -aryl) thiol (-SH), thiocyano (-SCN), Tosyl (CH ₃C₆H₄SO₂-)、C_3-12 cycloalkyl, C _2-12 alkenyl, C _5-12 cycloalkenyl, C _6-12 aryl, C _7-13 arylalkylene, C _4-12 heterocycloalkyl, and C _3-12 heteroaryl replace hydrogen, provided that the normal valence of the substituted atom is not exceeded. The indicated number of carbon atoms in the group does not include any substituents. For example, -CH ₂CH₂ CN is a C ₂ alkyl group substituted with a nitrile.

Although particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are presently unforeseen or unanticipated may be appreciated by those skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A polycarbonate composition comprising:

Linear homopolycarbonates and optionally styrene-containing copolymers;

A poly (carbonate-siloxane) comprising about 10wt% to about 30wt% siloxane, present in an amount effective to provide a siloxane content of about 1wt% to about 6wt%, based on the total weight of the polycarbonate composition;

An ultra-high molecular weight polydimethylsiloxane present in an amount effective to provide greater than about 0.3wt% to less than about 0.9wt% of a siloxane based on the total weight of the composition, wherein the weight average molecular weight of the polydimethylsiloxane is at least 100,000 g/mole as determined by gel permeation chromatography according to polystyrene standards, and

Flame retardant, and

Optionally, up to about 5wt% of an additive composition,

Wherein the linear homopolycarbonate, the optional styrene-containing copolymer, the poly (carbonate-siloxane), the ultra-high molecular weight polydimethylsiloxane, the flame retardant, and the optional additive composition total 100wt%.

2. A polycarbonate composition comprising:

about 65 to about 95 weight percent of a linear homopolycarbonate and optionally a styrene-containing copolymer;

A silicone content of poly (carbonate-silicone) comprising from about 10wt% to about 30wt% silicone, present in an amount effective to provide a silicone content of from about 1wt% to about 6wt%, based on the total weight of the polycarbonate composition;

Flame retardant, and

Optionally, up to about 10wt% of the additive composition, wherein the linear homopolycarbonate, the optional styrene-containing copolymer, the poly (carbonate-siloxane), the ultra-high molecular weight polydimethylsiloxane, the flame retardant, and the optional additive composition total 100wt%.

3. The polycarbonate composition of claim 1, wherein,

The calculated weight percentages of bromine and chlorine content of the polycarbonate composition are each about 900ppm or less and the calculated weight percentage of the total halogen content of the polycarbonate composition is about 1500ppm or less, or

The calculated weight percentages of bromine, chlorine, and fluorine content of the polycarbonate composition are each about 900ppm or less, and the calculated weight percentages of the total bromine, chlorine, and fluorine content of the polycarbonate composition are about 1500ppm or less.

4. The polycarbonate composition of claim 1, wherein a molded sample comprising the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 millimeters or less.

5. The polycarbonate composition of any of the preceding claims, wherein the poly (carbonate-siloxane) comprises repeating diorganosiloxane units of formula (10)

6. The polycarbonate composition of any of the preceding claims, wherein the linear homopolycarbonate is a bisphenol a polycarbonate homopolymer comprising:

A linear bisphenol A polycarbonate homopolymer having a weight average molecular weight of 15,000 to 25,000g/mol, preferably 17,000 to 25,000g/mol, as determined by gel permeation chromatography based on polystyrene standards and calculated for the polycarbonate, or

A linear bisphenol A polycarbonate homopolymer having a weight average molecular weight of 26,000 to 40,000g/mol, preferably 27,000 to 35,000g/mol, as determined by gel permeation chromatography according to polystyrene standards and calculated for the polycarbonate, or

A combination thereof.

7. The polycarbonate composition of any of the preceding claims, wherein the poly (carbonate siloxane) comprises bisphenol a carbonate repeat units and poly (dimethylsiloxane) repeat units.

8. The polycarbonate composition of any of the preceding claims, wherein poly (carbonate siloxane) has a siloxane content of about 15wt% to about 25wt%, based on the total weight of the poly (carbonate siloxane).

9. The polycarbonate composition of any of the preceding claims, wherein the flame retardant comprises an alkyl sulfonate, an aromatic sulfonate, an organophosphorus compound, or a combination thereof.

10. The polycarbonate composition of any of the preceding claims, wherein the flame retardant is not halogenated.

11. The polycarbonate composition of any of the preceding claims, wherein the styrene-containing copolymer is present and comprises an elastomeric phase comprising (i) butadiene and having a glass transition temperature of less than 10 ℃, and (ii) a rigid polymer phase having a glass transition temperature of greater than 15 ℃ and comprising a copolymer of a styrene-containing monovinylaromatic monomer and an unsaturated nitrile.

12. The polycarbonate composition of any of the preceding claims, wherein the composition does not include a halogenated anti-drip agent, preferably a fluorinated anti-drip agent.

13. A method of making the polycarbonate composition of any of the preceding claims, the method comprising melt mixing the components of the composition.

14. The method of claim 13, further comprising molding, casting, or extruding the composition to provide an article.

15. An article comprising the polycarbonate composition of any of the preceding claims.